CN100448645C

CN100448645C - Process for making a plastic moulded article with a metallized surface

Info

Publication number: CN100448645C
Application number: CNB038233444A
Authority: CN
Inventors: 约翰内斯·雅各布斯·贡斯; 理查德·雅克·特奥多尔·弗里森
Original assignee: DSM IP Assets BV
Current assignee: DSM IP Assets BV
Priority date: 2002-10-01
Filing date: 2003-09-29
Publication date: 2009-01-07
Anticipated expiration: 2023-09-29
Also published as: KR20050059225A; EP1405707A1; EP1545857A1; US20050269740A1; JP4434958B2; WO2004030890A1; JP2006501087A; DE60320568T2; ATE393006T1; EP1545857B1; AU2003269722A1; DE60320568D1; KR101007444B1; CN1856393A

Abstract

The invention relates to a process for making a plastic moulded article with a metallized surface, comprising the steps of introducing a metallized film in a mould and filling the mould with a plastic composition by means of injection moulding, with the metallized film comprising at least one layer consisting essentially of a thermoplastic elastomer containing polyether segments. Advantages of this process are amongst other things that a 3-dimensional (3-D) metallized moulded article may be made with the film adequately adhering everywhere to the plastic composition, and that the moulded article can also be provided with a surface with soft-touch properties. The invention also relates to a plastic moulded article with an at least partially metallized surface and to such an article that is further provided with laser markings.

Description

Manufacturing has the method for the moulded goods of metalized surface

Technical field

The present invention relates to make the method for the moulded goods that has metalized surface, comprise the steps:

(c) metalized film is imported in the mould; And

(d) by filled plastics composition in this mould of injection mo(u)lding normal direction.

The invention still further relates to moulded goods that has metalized surface and the metallization mechanograph that also is provided with laser labelling, and the end product that comprises this mechanograph.

Background technology

From the known this method of patent application WO 98/51516A1.This publication discloses the method for utilizing decorative metallized film to produce adornment.In this publication, decorative metallized film is based on the mixture of fluororesin.Fluororesin is because their anti-pollution and non-viscosity and by known.For decorative metallized film and substrate are adhered to well, additional adhesion layer is used to improve the adhesion between decorative metallized film and the substrate.

The shortcoming of the described known method of WO 98/51516A1 is: have to use adhesion layer to obtain to have three-dimensional (3-D) mechanograph of metalized surface, wherein metalized film shows the abundant adhesion with plastics composite, and in other place that edge and this film fully are out of shape also like this.

The purpose of this invention is to provide and a kind ofly can not show aforesaid drawbacks, or reveal the method for this shortcoming with much lower table of degree.

Unexpectedly, this purpose has been realized by the method according to this invention, uses metalized film in this method, and this film comprises the layer that one deck at least is made up of the thermoplastic elastomer (TPE) that contains polyether segment substantially.

This film of the layer that one deck at least is made up of the thermoplastic elastomer (TPE) that contains polyether segment substantially that comprises can metallize with the metal level that this film is shown good adhesion, and the thermoplastic elastomer (TPE) that contains polyether segment shows good adhesion to the whole lip-deep plastics composite of non-planar article.

EP 0296108 A1 discloses the method that a kind of manufacturing has the moulded goods of decorative surface, has wherein used copolyether amide (copolyether amide) film, but that this film does not have is decorated, particularly is not metallized in advance.In this known mould interior trim (IMD) method, when mould is filled, by under the effect of heat, transfer is decorated the copolyether amide film from the printing ink of ornamental supporting film, this supporting film is sent in the mould with the copolyether amide film, but can not form the part of decorated mechanograph.

Summary of the invention

In the method according to the invention, technology by various known various dissimilar thin metal layers of coating, film can be metallized in advance, and this film can be used as it is makes three-dimensional (3-D) mechanograph, this film still presents the abundant adhesion to plastics composite simultaneously, and need not use additional adhesion layer.Known metallization technology, for example electroless plating, metal spraying, sputter or vacuum metallization processes all have description in many handbooks, Encyclopaedia of Polymer Science andEngineering for example, vol.9, p.580-622, Mark etc., John Wiley and Sons (1987), ISBN 0-471-80941-1.Dissimilar metals comprises copper, silver, gold, chromium, nickel, aluminium, iron, tin, zinc, lead and brass as an example.Metal level can be partly, fully or with the form of pattern or conduction path come the coverlay surface.Metal layer thickness depends on application requirements and the technology that is adopted, but generally in 0.002～45 micrometer range.For example, EMI shielding often use than those emphasize to reflect or only the application need of decorative effects thicker layer.

Another advantage of the method according to this invention is: this film also remains intact in the place that those mechanographs that do not have this film have opening, the place of button for example will be installed in those follow-up phases, thereby for example can form waterproof (spattering) or dustproof shell for the product that has contact knob or button etc.Another advantage is in special embodiment, wherein metalized surface is facing to the plastics composite surface, and the surface of moulded goods is that the thermoplastic elastic side by metalized film forms, the surface of gained mechanograph has the sensation of pleasant, and promptly it has so-called flexible touch characteristics.And this surface also can be quite coarse, and promptly it can present non-slip properties.This is particularly conducive to for example application of the shell of end product (for example mobile phone, pocket calculating machine, communicator or personal digital assistant, kitchen tools etc.), and help the delivery vehicle member, the particularly member in the compartment, for example instrument board or its parts.

Here metalized film be interpreted as representing a side at least by localized metallicization and play and provide technical characteristic especially and be not only the film that the effect of different outward appearances is provided for mechanograph.The characteristic that possesses skills for example is interpreted as in the conducting path of circuit or the electricity of guided modes member made or hot as required in for the heat shielding that prevents hot spot on the product surface; For example reverberation or electromagnetic wave in the so-called EMI of lamp reflector, shield electromagnetic interference shielding respectively; For example provide diffusion barrier by the anti-gas (for example oxygen) or the metal level of moisture diffusion.And this method can provide wear-resisting metalized surface, and this metalized surface is coated with thermoplastic elastomer films thus, for example is used to make automobile door handle.Under one situation of back, metalized film is imported in the mould in the step of the method according to this invention by this way, be the surface of the thermoplastic polymer surface of film facing to mould, and the metalized surface of film is facing to the inside of mould, in the step of the process of filling mould with plastics composite, this metalized surface contacts plastics composite surface thus.In such embodiments, wherein plastics composite contacts with the metalized surface of film, rather than contacts with non-metallic surface, can further strengthen adhesion by using adhesion promoter or adhesion layer.

This film not only can have the color that is different from mechanograph, and special color effect can be provided, for example metal appearance or different gloss, especially when this film only when partially metallised, if perhaps the metalized surface of film is facing to plastics composite.

Except being metallized to small part, this film also can provide one or more patterns, image or mark, and these can only be used for modifying, and only are used to provide information or both to have both at the same time.This film can be transparent or translucent, but also can (almost) be opaque.This film can be an atresia, or has certain porosity, and it can have smooth surface, and can the application surface texture.

Substantially the layer of being made up of the thermoplastic elastomer (TPE) that contains polyether segment here is interpreted as representing: this layer makes by comprising the composition of at least a thermoplastic elastomer (TPE) that contains polyether segment as its key component, be said composition generally comprise account for this total composition greater than 50 quality %, preferably comprise greater than 60%, more preferably comprise, even more preferably comprise this thermoplastic elastomer (TPE) greater than 80% greater than 70%.Said composition also can contain other polymer up to 50 quality %, preferably is no more than 40%, more preferably no more than 30%, even more preferably no more than 20%; Thereby this at least a thermoplastic elastomer (TPE) forms the continuous phase of said composition.Preferably, this other polymer is compatible with this thermoplastic elastomer (TPE), keeps or improves machinery and aesthetic properties.Said composition can also comprise the additive of any routine, for example stabilizing agent, colouring agent, processing aids or flame-retardant compound.Generally speaking, these additives account for 0.01～10 quality % of total composition respectively according to its function.

The suitable example that contains the thermoplastic elastomer (TPE) of polyether segment for example is the block copolymer that has so-called hard segment and soft chain segment, and wherein soft chain segment is a polyethers, preferably aliphatic polyether.Be also referred to as thermoplastic elastomer (TPE) or copolymer below this thermoplastic elastomer (TPE) that contains polyether segment.Preferably, soft chain segment comprises the polyethers of being derived by at least a alkylene oxide, for example poly-(alkylene oxide) glycol.This copolymer all presents the favorable mechanical performance in the temperature range of non-constant width.As for poly-(alkylene oxide) glycol, for example can use poly-(tetrahydrofuran) glycol or poly-(oxolane) glycol, particularly poly-(1, the 2-expoxy propane) glycol of poly-(expoxy propane) glycol, poly-(oxirane) glycol, ethylene oxide-capped poly-(expoxy propane) glycol or their combination.Such polyethers has essentially amorphous feature, lower glass transition temperatures (T _g) and low rigidity.Preferably, T _gBe lower than 0 ℃, more preferably be lower than-20 ℃, most preferably be lower than-30 ℃.Its advantage is this block copolymer even high flexibility at low temperatures and favorable mechanical performance.The molecular weight of these soft chain segments is generally 400～6000g/mol, is preferably 500～3000g/mol.

The softening temperature of the hard segment in this copolymer, promptly glass transition temperature or melt temperature generally are higher than 100 ℃, more preferably are higher than 150 ℃, even more preferably are higher than 170 ℃.Preferably, this hard segment has the semi-crystalline state feature, and the result improves the chemical resistance of copolymer.Suitable hard segment is based on the segment of polyurethane, polyamide or polyester.The advantage of this copolymerization ether urethane, copolyether amide or copolyether ester thermoplastic elastomer (TPE) is that they allow to produce the film with good character, and this film is transparent or translucent at least, can be owing to the result who foams in the film-forming process but porous, and can easily be metallized by various technology.

Contain that the ratio between the soft chain segment and hard segment generally can change in the thermoplastic elastomer (TPE) of polyether segment between grace period, but especially will select based on desired copolymer hardness.Hardness is generally between 20 and 80 Shore D.The advantage of soft is that it forms more flexible film, and high rigidity generally provides better heat-resisting quantity and better engineering properties.Preferably, this hardness is between 30 and 75, more preferably between 35 and 70 Shore D.Its advantage is to obtain good balance between heterogeneity, and described heterogeneity for example is machinability, temperature tolerance, mechanical performance and if desired, by the impressionability of various technology.

Preferably, this copolymer is a copolyether ester, because it has favourable processing characteristics.More specifically, the polyester formed by at least a alkylene glycols and at least a aromatic dicarboxylic acids or its ester institute repeat units derived of hard segment.This alkylene group generally comprises 2～6 carbon atoms, preferably comprises 2～4 carbon atoms.As for alkylene glycols preferably ethylene glycol, propane diols, particularly 1, the 4-butanediol.Terephthalic acid (TPA), 1,4-naphthalene dicarboxylic carboxylic acid or 4,4-biphenyl acid are particularly suitable for as the aromatic dicarboxylic acids.If desired, for example other dicarboxylic acids of M-phthalic acid also can exist, and this generally causes fusing point lower.Preferably, hard segment is substantially based on PETG, PTT, particularly based on polybutylene terephthalate (PBT).Its advantage is good crystallization behavior and high fusing point, thereby this copolymer can easily processed film forming, and presents good heat endurance and chemical stability.

The example of this copolymer, particularly copolyether ester and preparation example be as at Handbook ofThermoplastics, etc.O.Olabishi, and Chapter 17, Marcel Dekker Inc., New York1997, ISBN 0-8247-9797-3; Thermoplastic Elastomers, 2nd Ed, Chapter 8, Carl Hanser Verlag (1996) ISBN 1-56990-205-4; Encyclopedia of PolymerScience and Engineering, Vol.12, Wiley﹠amp; Sons, New York (1998), ISBN 0-471-80944, p.75-117 and description all arranged in the document of wherein being quoted.

Obtained the extraordinary film that is made by at least a copolyether ester of result, this copolyether ester has hard segment of being derived by polybutylene terephthalate (PBT) and the soft chain segment of being derived by poly-(tetrahydrofuran) glycol or ethylene oxide-capped poly-(expoxy propane) glycol.The advantage of these copolymers is hear resistance and processing behaviors of their excellences.Found in the method according to the invention, when mould is filled the polymer composition of fusion, even its initial temperature is higher than the fusing point of this copolyether ester, the film that is made by these materials can or not be can not soften fully or melt at least, thereby the gained mechanograph has the layer of copolyether ester on whole (desired part) surface.

Metalized film can be by utilizing known metallization technology, and the film that will comprise the layer that one deck at least is made up of the thermoplastic elastomer (TPE) that contains polyether segment substantially metallizes and obtains.And in the method according to the invention, this metalized film is found the excellent adhesion that presents mechanograph, and metalized surface is not subjected to the influence of injection mo(u)lding step simultaneously.

The surface that this film is metallized can be completely or partially, and for example the form with pattern is coated with metal.The example of pattern is the conduction path in the circuit.The design of the partially metallised or pattern (two dimension) on this film and use and to make the film that is taken place in the mechanograph (three-dimensional) in the step (b) can consider in the method according to this invention and be out of shape.

In specific embodiments, this film is translucent or transparent, thereby this film can be placed in the mould by this way, and a side that promptly is coated with metal contacts with plastics composite.Its advantage is that this metal level is still clearly visible on the goods with the method according to this invention gained, and can directly not be subjected to the influence or the wearing and tearing of environment.In this case, metal pattern preferably is coated on the film with mirror image.

In preferred embodiment of the process according to the invention, this metalized film is made up of the individual layer that has been metallized, comprise copolymer.Its advantage is that technology is simple.

In another embodiment of the process according to the invention, this film comprises two-layer at least, and wherein one deck skin is made up of copolymer substantially at least, and this layer is metallized.This multilayer film can make by coextrusion processes or by stacked several tunics.Its advantage is by different layers being used different materials, can obtaining desired film properties of combination.For example can select can be metallized preferably and provide the copolymer of the excellent adhesion of plastics composite and the combination that another kind for example presents the material of good surface properties (for example wear-resisting property).The example of this multilayer film is to have substantially the layer is made up of copolyether ester copolymer and the film of another layer of polycarbonate.The advantage of this combination is the excellent adhesion between the layer and the high glaze and the wearability of layer of polycarbonate.

In particular embodiment of the process according to the invention, combination by two-layer at least all substantially by copolymer forms but have different hardness layer.But it is selected because of its good metal voltinism that such advantage is a kind of component, and another kind of component is selected because of its another kind of desired character.The mechanograph of the metalized surface that for example has flexible touch and/or non-slip properties can be provided by this way.Flexible touch character generally can be by being made superficial layer and obtain to its coating particular surface texture by low-durometer material, described low-durometer material for example is hardness less than 60, preferably less than 50, be more preferably less than the copolymer of 40 Shore D.Example is that to comprise copolyether ester layer and the hardness that hardness is 40 Shore D be the film of the copolyether ester layer of 63 Shore D.

In another special embodiment of the process according to the invention, metalized film comprises the foaming layer that one deck at least is made up of the thermoplastic elastomer (TPE) that contains polyether segment substantially; That is to say that this layer has loose structure, preferably the blind hole structure.Its advantage is that the flexible touch character of this metalized surface can be further improved, and can obtain the resilience buffering effect.This has special importance for utensil and handheld device or other covering.By expressing technique, use composition for thermoplastic elastomer and chemistry or physical blowing agent can make perforated membrane.

Film thickness can change in grace period.Preferably, film thickness is greater than 0.01mm, because otherwise this film is difficult to handle, and this film is torn or wrinkling having a big risk when filling mould.This film preferably is thinner than 2 or 1mm, and this depends on hardness that it is shaped to the 3-D mechanograph easily and to the better adhesion of product surface.Therefore, this film thickness is preferably 0.01-1mm, and more preferably 0.05-0.75mm most preferably is 0.1-0.5mm.

Before in being directed to the mould of opening, under room temperature or low temperature, for example by cutting or compacting, for example freezing cutting can be made this metalized film suitable size.This cutting or compacting can be finished under the help of cutter, also can finish with for example water flow jet or laser beam.And, can be during injection mo(u)lding step (b) or just in time before this this film is made suitable size.Under latter event, this film for example can be delivered to mould and the injection molding machine from roller continuously.

Plastics composite can comprise the polymer of different chemical composition and character.Preferably, this plastics composite based on when filling mould its can with the perhaps miscible mutually polymer of copolymer in the film that is contacted.Composition based on a kind of polymer is understood that to represent that described polymer is the main component of said composition, that is to say, this polymer forms the continuous phase of said composition.Its advantage is to have obtained good adhesion between plastics composite and film.If use the film that contains copolyether amide, then this plastics composite is preferably based on for example polyamide.The advantage of copolymerization ether urethane film is that this film all shows good adhesion to various plastics.

And, have been found that in the method according to the invention and can improve adhesion by the temperature that improves mould.For this reason, mold temperature is at least 60 ℃, preferably is at least 90 ℃, more preferably is at least 120 ℃, most preferably is at least 140 ℃.But should be noted that for specific film and will avoid mold temperature too high, because this may cause the deterioration of existing image on the film for example, perhaps even cause the film fusing.

Under the situation of the film that contains copolyether ester, the suitable plastic composition is preferably based on thermoplastic polyester or Merlon, and is very good because film adheres to.Suitable polyester example comprises PETG (PET) and polybutylene terephthalate (PBT) (PBT) and their mixture.The example of polycarbonate plastic compositions comprises the composition based on bisphenol-a polycarbonate (PC) and copolymer and mixture.Suitable composition for example is the mixture of PC and PET (PC/PET), PC and PBT (PC/PBT), PBT and PET or PC and acrylonitrile/butadiene/styrene copolymer (PC/ABS).The advantage of this plastics composite is the mechanograph that can obtain to have approaching dimensional tolerance and very good dimensional stability in big temperature range, and this goods can be used as the shell of various utensils.

Particular of the present invention is to use the film contain copolyether ester and based on the method for the combination of the plastics composite of PBT composition or PC/ABS mixture.

In another embodiment of the process according to the invention, in step (b), fill mould with foamed plastic composition.Its advantage is to obtain low-density mechanograph.If used plastics composite has low modulus, then obtain soft, the mechanograph that also has measured, the fine and close metalized surface of matter.An example of this embodiment is wherein to abut against the copolyether ester film with polyurethane foam to fill mould.

In another suitable embodiment, but this film is a laser labelling, this for example is because this film contains at least a radiosensitive colouring agent, perhaps because metal level is radiosensitive, and can make mark thereon, wherein said colouring agent can changes colour under for example from the effect of the radiation of laser instrument." change color " comprises by a certain monochrome and is changed to another color, become by colourless state and have color or partially or completely fade.But the film of laser labelling can also comprise other additives that are used to improve laser labelling.The advantage of these measures is marks of adding or decorates and may be suitable for producing in batches mechanograph later on that these marks can be changed in simple relatively mode, and if desired, even can align the goods of being produced and change every one.This just can give for example a kind of personal characteristics of product or unique code of personal appliance (for example cell phone or personal digital assistant).

If this film comprises at least two kinds, preferred at least three kinds of radiosensitive colouring agents, then select type of laser radiation for example to allow to provide the mark of different colours even multicolor image, for example user's photo.

Can also not be the transparent or semitransparent film of mark by laser emission, but be marked at the plastics composite under this film, and the radiation of passing film by laser thereon, particularly apply image on the surf zone that is not covered by metal level.

The invention still further relates to the moulded goods that is metallized to small part that can obtain like this.Particularly, the present invention relates to have be metallized to small part, also have a mechanograph on the surface of flexible touch and/or non-slip properties.

The invention still further relates to and have the moulded goods that is metallized the surface to small part, can be coated on it by other mark of laser emission.Though its advantage be this film by 3 D deformation, can also provide image to mechanograph in any desired position and with high accuracy.Therefore, the invention still further relates to this through moulded goods mark, metallized.

The invention still further relates to the end product that comprises according to moulded goods of the present invention.At least a portion of this product surface is made up of this article according to the invention, particularly with technology or the relevant part of informedness/decorative function, for example control panel of product.That its advantage is that this end product is provided with is metallized, informedness surface alternatively, and this surface for example seldom is worn.Another advantage is that this end product can be by the image of laser labelling with the individual character of uniqueness.Also having an advantage is that this end product also can have flexible touch and/or non-slip properties.

The example of end product comprises the control panel of the three dimensional molded interconnect equipment (3-DMID) that contains the conductive metal path, molded case circuit plate (MCB), the lamp reflector that is used for family expenses/industrial utensil or automobile, consumption electronic product and has the shell that is used for the shielding metal level of EMI.

The specific embodiment

With reference to the following examples the present invention is described.

Film

Under the help of general extruder with 45mm screw rod and planar film ancillary equipment, by

EM550: hardness is about the copolyether ester of 55 Shore D, and (DSM EngineeringPlastics NL) makes the film of thickness near 150 μ m.

Example I

From by

Downcut the circular sample that diameter is about 78mm in the film that EM550 makes.This sample is placed in the Cressington flush coater (model 108 Auro), and pressure is reduced to about 10Pa subsequently.Argon gas is used to wash this flush coater.In 300 seconds, the function of current of 30mA is to flush coater, and the gold layer of about 150nm is applied on this sample.

This sample that scribbles golden film is directed in the mould of opening, and its gold surface is facing to the surface of mould.This mould comprises the single die cavity of the plate that is used to be of a size of 70*50mm, and wherein the thickness of this plate progressively reduces to 1mm from 3mm to 2mm.This varied in thickness causes the staged surface of this plate, and has wedge angle at the transition position from a kind of thickness to another thickness.By oily thermostat this mould is remained under 120 ℃ the temperature, and this mould is installed to and is had in the Engel 80A injection machine of Universal screw rod that diameter is 22mm.

After closed mould, die cavity be filled fusion, model is

The PC/ABS plastics composite of CM 206 (DSM Engineering Plastics, NL), said composition under 90 ℃, in air circulating oven by predrying 6 hours.The temperature of injection machine from the feed hopper to the nozzle is set to 240-250-2550-250 ℃; Fusion time was near 5.5 seconds, and inject time, cool time, circulation timei was near 28 seconds near 20 seconds near 1.08 seconds.The injection volume of plastics composite is near 13g.These settings are consistent with the proposed standard processing conditions of this material.

In case from mould, shift out mechanograph, find that promptly all there is gold-plated film in the whole surface of this mechanograph, comprise lip-deep edge, and do not see and tear, fold or other defective.This film shows the good adhesion to surface plate, and can not it be moved apart the plate surface by scraping or tearing.

Example II

Be similar to example II, make mechanograph, but in this case (PBT with 20 quality % glass fibres, DSM Engineering Plastics NL) is used as plastics composite to TV4 240.In forming process, use 80 ℃ mold temperature, and are about plasticizing, injection, cooling and circulation timei 5.9 seconds respectively, 1.07 seconds, 20 seconds and 28 seconds.All mechanographs all have aforesaid outward appearance.

This film shows the good adhesion to the plate surface, and only is difficult to it is moved apart the plate surface by scraping or tearing.

EXAMPLE III

Be similar to example II, by

TV4 240 makes mechanograph, but uses 120 ℃ mold temperature in forming process.

All mechanographs all have aforesaid outward appearance.This film shows the very good adhesion to the plate surface.Substantially can not film be torn off the surface with hand, in case adhere to so consequently membrane, this film promptly begins to tear.

Claims

1. a manufacturing has the method for the moulded goods of metalized surface, comprises the steps:

(a) metalized film is imported in the mould; And

(b) by injection mo(u)lding filled plastics composition in this mould;

It is characterized in that described metalized film comprises the layer that one deck at least is made up of the thermoplastic elastomer (TPE) that contains polyether segment substantially.

2. the method for claim 1, the hardness of wherein said thermoplastic elastomer (TPE) is between 30 and 75 Shore D.

3. method as claimed in claim 1 or 2, wherein said thermoplastic elastomer (TPE) is a copolyether ester.

4. method as claimed in claim 3, wherein said copolyether ester comprises the hard segment based on polybutylene terephthalate (PBT).

5. method as claimed in claim 1 or 2, wherein said thermoplastic elastomer (TPE) comprise the soft chain segment of being derived by poly-(tetrahydrofuran) glycol or ethylene oxide-capped poly-(expoxy propane) glycol.

6. method as claimed in claim 1 or 2, wherein said film is metallized by vacuum metallization methods.

7. method as claimed in claim 1 or 2, wherein said film are transparent or translucent.

8. method as claimed in claim 1 or 2, wherein said film is made up of individual layer, and described individual layer is made up of the thermoplastic elastomer (TPE) that contains polyether segment substantially.

9. method as claimed in claim 1 or 2, wherein said film comprises two-layer at least, wherein skin comprises the thermoplastic elastomer (TPE) that contains polyether segment at least, and has been metallized.

10. method as claimed in claim 9, wherein said two-layer at least wherein every layer all basic by containing polyether segment but the different thermoplastic elastomer (TPE) of hardness form.

11. method as claimed in claim 1 or 2, the thickness of wherein said film is 0.05-0.75mm.

12. method as claimed in claim 1 or 2, wherein use based on the described thermoplastic elastomer (TPE) that the contains polyether segment plastics composite of perhaps miscible polymer mutually.

13. method as claimed in claim 12, wherein said plastics composite are based on thermoplastic polyester and/or Merlon, and described thermoplastic elastomer (TPE) is a copolyether ester.

14. method as claimed in claim 13, wherein said plastics composite are thermoplastic polyester or polycarbonate compositions.

15. method as claimed in claim 1 or 2, but wherein said film is a laser labelling.

16. method as claimed in claim 1 or 2, but wherein said plastics composite is a laser labelling.

17. method as claimed in claim 1 or 2, wherein said metalized film is introduced in the described mould facing to the mode of described plastics composite with its surface that is not metallized.

18. moulded goods that obtains according to each described method of aforementioned claim with metalized surface.

19. the moulded goods with metalized surface as claimed in claim 18, described surface also has flexible touch and/or non-slip properties.

20. one kind has a plastic capable of laser labelling mechanograph that is metallized the surface to small part according to what claim 15 or 16 described methods obtained.

21. moulded goods that is metallized the surface according to having of obtaining of claim 15 or 16 described methods to small part and is provided with laser labelling.

22. one kind comprises the end product according to each described moulded goods of claim 18-21.